RU2352593C2 - Polyurethane foam made of hydroxymethyl-containing polyesterpolyols - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention refers to method for making bulk, high resilience slabstock or moulded foam, used for upholstery, automobile seats and panel cushions, for packing, other applications to softening and energy management, for sealing and other applications. The presented method involves as follows. Organic polyisocyanate contacts with polyol compound containing high mass equivalent polyol or mixed polyols with foaming agent, gelling catalyst and surface-active substance added. At least 10 wt % of high mass equivalent polyol (polyols) represent one or more equivalent mass hydoxymethyl-containing polyesterpolyols at least 400 up to 15000 produced by interaction of hydoxymethyl group containing fatty acid with 12-26 carbon or this acid ester atoms and compound initiator polyol or polyamine, thereby polyesterpolyol contains as follows: [H-X]_(n-p)-R-[X-Z]_p, where R is residual compound initiator, X is independent, -O-, -NH- or -NR'-, while Z- represents linear or branched chain containing one or more groups A, independently chosen of groups A1, A2, A3, A4 and A5, expressed by formulas (II), (III), (IV), (V) and (VI), respectively. Besides there is disclosed polyurethane foam made by the declared method. Declared method ensures making polyurethane foams with using polyol from renewable source.

EFFECT: improved UV resistance and heat stability, and improved gas-invoked discoloring resistance.

9 cl, 8 tbl, 41 ex

Description

The invention relates to flexible polyurethane foams and a method for producing such foams.

Polyurethane foams are prepared by reacting polyisocyanates and polyols. The first production of polyurethane foams on an industrial scale appeared using polyester polyols obtained by the ester condensation reaction of diols or polyols and dicarboxylic acids to produce flexible foams. Complex polyester polyols were replaced by simple polyether polyols due to their lower cost and the ability to obtain a wide range of polyols. Polyethers are prepared by the polymerization of epoxides (oxiranes) derived from petroleum feedstocks in the presence of initiator compounds that contain starting compounds with active hydrogen, such as low molecular weight polyols and polyamines. Rigid polyurethane foams were obtained with castor oil or castor oil by-products.

There have been attempts to obtain polyols from plant or renewable raw materials such as disclosed by Peerman et al. In US Pat. Nos. 4,423,162, 4,496,487 and 4,543,369. Peerman et al. Describe hydroformylation and reduction of fatty acid esters that are derived from vegetable oils and the formation of esters the resulting hydroxylated materials with a polyol or polyamine. However, Peerman et al. Specifically describe gelation problems that they suggest avoiding using no more than 1 mole of hydroxymethylated material per equivalent of polyol or polyamine. Therefore, esters according to Peerman et al. Are materials of low equivalent weight, which, as has been shown, are applicable only for the preparation of crosslinked rigid polyurethanes.

Thus, it would be desirable to propose a flexible polyurethane foam having good properties, which would also be obtained from a polyol based on a renewable source.

The present invention relates to a method for producing a polyurethane foam comprising contacting an organic polyisocyanate with a polyol composition containing a high equivalent weight polyol or a mixture of high equivalent weight polyols in the presence of a foaming agent and a surfactant under conditions when the polyisocyanate interacts with the polyol composition, and the foaming agent forms a gas to produce a cellular polyurethane and / or polyurea-based polymer, where at least 10% by weight of the polyol (by Liols) of high equivalent weight is one or more hydroxymethyl-containing polyester polyols obtained by reacting a hydroxymethyl group-containing fatty acid having 12-26 carbon atoms, or an ester of such a hydroxymethyl group-containing fatty acid with an initiating compound, namely a polyol or polyamine, having an average of at least 2 hydroxyl, primary amino groups and / or secondary amino groups, so that the hydroxymethyl-containing polyester polyol contains an average of at least 1.3 repeating units derived from a hydroxymethyl group-containing fatty acid or ester per total number of hydroxyl, primary amino groups and secondary amino groups on the initiator compound, and the hydroxymethyl-containing polyester polyol has an equivalent weight of at least 400 and up to 15,000.

It is unexpected that good quality flexible polyurethane foams can be prepared using these complex polyester polyols in a wide range of concentrations using processes and compositions that in many cases closely resemble those used to make conventional polyurethane foams based on simple polyether polyols. This is feasible even when the molecular structure of these polyester polyols is prone to greater variability (among the molecules in the polyester polyol sample) than the structure of polyether polyols with respect to the branching, positioning and spatial position of the reactive (hydroxyl) groups and the composition of the repeating units. In addition, the resulting foam often exhibits some improved properties compared to conventional polyether polyol foams, including improved UV resistance, improved gas bleaching resistance, and improved heat resistance.

The polyol component contains one or more polyols of high equivalent weight. By "high equivalent weight polyol" is meant a polyol having an atomic mass of at least 400 times the total number of hydroxyl, primary amino groups and secondary amino groups on the polyol molecule.

The hydroxymethyl-containing polyester polyol has an average of at least 2, preferably at least 2.5, more preferably at least 2.8 and up to about 12, more preferably up to about 6, even more preferably up to about 5 hydroxyl, primary amino groups and secondary amino groups in total per molecule. The hydroxymethyl-containing polyester polyol has an equivalent weight of at least 400, such as at least about 600, at least about 650, at least about 700, or at least about 725, and up to about 15,000, such as, for example, up to about 6000, up to about 3500, up to about 1700, up to about 1300 or up to about 1000. The equivalent mass is equal to the number average molecular weight of the molecule, divided by the total number of hydroxyl, primary amino groups and secondary amino groups.

A hydroxymethyl-containing polyester polyol is usually prepared by reacting a hydroxymethyl group-containing fatty acid having 12-26 carbon atoms, or an ester of such a hydroxymethyl group-containing fatty acid with an initiating compound, namely a polyol, hydroxylamine or polyamine having an average of at least 20 hydroxyl primary amino groups and / or secondary amino groups per molecule. The relative proportions of the starting materials and the reaction conditions are selected so that the resulting hydroxymethyl-containing polyester polyol contains at least 1.3 repeating units derived from a hydroxymethyl group-containing fatty acid or its ester, for each hydroxyl, primary amino group and secondary amino group on the compound- initiator, and containing hydroxymethyl complex polyester polyol has an equivalent weight of at least 400 up to about 15000.

Hydroxymethyl-containing polyester polyol is preferably a mixture of compounds having the following average structure:

,

,

where R represents the remainder of the initiator compound having n hydroxyl, primary amino groups and / or secondary amino groups, where n is at least two, each X is independently —O—, —NH— or —NR′—, where R ′ is inert a substituted alkyl, aryl, cycloalkyl or aralkyl group, p is a number from 1 to n representing the average number of [XZ] groups per molecule of a hydroxymethyl complex polyester polyol, Z is a linear or branched chain containing one or more groups A, provided that average number of groups A per molecule is a quantity that exceeds n by ≥1.3 times, and each A is independently selected from the group consisting of A1, A2, A3, A4 and A5, provided that at least some groups A are A1, A2 or A3 . A1 is represented by the formula:

,

,

where B represents H or a covalent bond with a carbonyl carbon atom of another group A, m represents a number greater than 3, n is greater than or equal to zero, and m + n is from 8 to 22, especially from 11 to 19. A2 is represented by the formula:

,

,

where B represents the same as above, v represents a number greater than 3, r and s represent numbers greater than or equal to zero, and v + r + s is from 6 to 20, especially from 10 to 18. A3 is represented the formula:

,

,

where B, v, each r and s have the above meanings, t represents a number greater than or equal to zero, and the sum of v, r, s and t is from 5 to 19, especially from 10 to 18. A4 is represented by the formula:

,

,

where w is 10-24, and A5 is represented by the formula:

,

,

where R 'represents a linear or branched alkyl group which is substituted by at least one cyclic ether group and optionally one or more hydroxyl groups or other ether groups. The cyclic ether group may be saturated or unsaturated and may contain another inert substitution. Hydroxyl groups may be on an alkyl chain, or on a cyclic ether group, or on both of them. The alkyl group may contain a second terminal group —C (O) - or —C (O) O— through which it can be attached to another initiator molecule. Groups A5 are typically represented by lactols, lactones, saturated or unsaturated cyclic ethers or dimers, which are formed as impurities during the production of a hydroxymethyl group-containing fatty acid or ester. A5 groups may contain 12-50 carbon atoms.

In the formula I, n is preferably 2-8, more preferably 2-6, even more preferably 2-5, and especially from about 3 to 5. Each X is preferably —O—. The total average number of groups A per hydroxymethylated polyol molecule is preferably at least 1.5 times n, for example from about 1.5 to about 10 times n, from about 2 to about 10 times n, or from about 2 up to about 5 times the value of n.

A is preferably A1, a mixture of A1 and A2, a mixture of A1 and A4, a mixture of A1, A2 and A4, a mixture of A1, A2 and A3 or a mixture of A1, A2, A3 and A4, in each case optionally containing a certain amount of A5. Mixtures A1 and A2 preferably contain groups A1 and A2 in a molar ratio from 10:90 to 95: 5, especially from 60:40 to 90:10. Mixtures A1 and A4 preferably contain groups A1 and A4 in a molar ratio of 99.9: 0.1 to 70:30, especially in a ratio of 99.9: 0.1 to 85:15. Mixtures A1, A2 and A4 preferably contain from about 10 to 95 molar percent of groups A1, 5-90 percent of groups A2 and up to about 30 percent of groups A4. More preferred mixtures of A1, A2 and A4 contain about 25-70 mol% of groups A1, 15-40% of groups A2 and up to 30% of groups A4. Mixtures of groups A1, A2 and A3 preferably contain from about 30 to 80 mol.% A1, 10-60% A2 and 0.1-10% of groups A3. Mixtures of groups A1, A2, A3 and A4 preferably contain from 20 to 50 molar percent of A1, from 1 to about 65 percent of A2, from 0.1 to about 10 percent of A3, and up to 30 percent of groups of A4. Particularly preferred polyester polyols according to the invention contain a mixture of about 20-50% of groups A1, 20-50% of groups A2, 0.5-4% of groups A3 and 15-30% of groups A4. In all cases, groups A5 mainly comprise from 0 to 7%, especially from 0 to 5% of all groups A.

Preferred mixtures of groups A typically contain on average from about 0.8 to about 1.5 groups —CH ₂ O— per group A, such as, for example, from about 0.9 to about 1.3 groups —CH ₂ O— on group A or from about 0.95 to about 1.2 groups —CH ₂ O— per group A. Such mixtures of groups A (1) allow the functionality of the polyester polyol to be controlled mainly by the functionality of the initiator and (2) tend to form less densely branched polyester polyols.

"Inertly substituted groups" are groups that do not interact with isocyanate groups and which otherwise do not participate in adverse reactions during the preparation of the hydroxymethyl group-containing polyester polyol. Examples of such inert substituents include aryl, cycloalkyl, silyl, halogen (especially fluorine, chlorine or bromine), nitro, ether, ester and the like.

Hydroxymethyl-containing polyester polyols corresponding to structure I can be obtained in a multistep process from vegetable or animal fats that contain one or more carbon-carbon double bonds in at least one component of the fatty acid chain. Suitable fats include, for example, chicken fat, canola vegetable oil, citrus seed oil, cocoa butter, cottonseed oil, lard, linseed oil, oatmeal oil, olive oil, palm oil, peanut oil, rapeseed oil, rice bran oil, safflower oil, sesame oil, soybean oil, sunflower oil or beef tallow.

Plant or animal fat is first transesterified with a lower alcohol, especially methanol or ethanol, to produce alkyl esters of constituent fatty acids. The resulting alkyl esters can be hydrolyzed to the corresponding fatty acids, if desired, but this step is usually not necessary or desirable. Alkyl esters (or fatty acids) are simply hydroformylated by reaction with carbon monoxide and hydrogen. This introduces —CHO groups into the fatty acid chain at the site of the carbon-carbon unsaturation. Suitable hydroformylation processes are described, for example, in US Pat. Nos. 4,731,486 and 4,631,021 and in provisional patent application US 60/465663, filed April 25, 2003, all incorporated by reference. Some fatty acid groups contain numerous sites with carbon-carbon double bonds. In such cases, the hydroformylation reaction cannot introduce —CHO groups at all double bond sites. The subsequent hydrogenation step converts the —CHO groups to hydroxymethyl groups (—CH ₂ OH), while the hydrogenation of the residual carbon-carbon bonds eliminates substantially all of the carbon-carbon unsaturation. The resulting mixture of hydromethylated fatty acids is then reacted with an initiator compound to remove water or a lower alcohol to form a polyester polyol.

The initiator contains two or more hydroxyl, primary amino groups or secondary amino groups, it may be a polyol, alkanolamine or polyamine. The initiators of particular interest are polyols. Suitable initiators are simple polyether polyols, including ethylene oxide and / or propylene oxide polymers having 2-8, especially 2-4 hydroxyl groups per molecule and a molecular weight of about 150-3000, especially 200-1000.

Hydroxymethyl-containing fatty acids obtained in this process tend to be a mixture of materials having no hydroxymethyl groups and materials having 1, 2 or 3 hydroxymethyl groups. The relative fraction of materials having 2 and 3 hydroxymethyl groups is usually slightly lower than the relative fraction of the starting fatty acids (or alkyl esters) containing 2 and 3 carbon-carbon double bonds, since the hydroformylation reaction often does not take place on all carbon-carbon double bonds if you do not comply with strict conditions. Carbon-carbon double bonds that are not hydroformylated usually become hydrogenated.

Methods for the preparation of hydroxymethyl-containing polyester polyols are described in provisional patent application US 60/465663, filed April 25, 2003, incorporated by reference.

The hydroxymethyl-containing polyester polyol thus obtained typically contains some unreacted initiator compound and may contain unreacted hydromethylated fatty acids (or esters). Initiator compounds often interact with only one functionality or two functionalities with fatty acids (or esters), and the resulting polyester polyol often contains free hydroxyl or amino groups linked directly to the residue of the initiator compound.

The hydroxymethyl-containing polyester polyol can be alkoxylated, if desired, to introduce polyether chains to one or more hydroxymethyl groups. The hydroxymethyl-containing polyester polyol may also be aminated by reaction with ammonia or a primary amine followed by hydrogenation to replace the hydroxyl groups with primary or secondary amino groups. Primary or secondary amino groups can also be introduced by attaching the diisocyanate at the ends of the polyester polyol and then converting the terminal isocyanate groups thus introduced into the amino groups by reaction with water.

The polyol composition used to produce the foam may additionally contain one or more additional polyols of high equivalent weight other than the hydroxymethyl-containing polyester polyol. Such suitable additional high equivalent weight polyols include polyether polyols and polyester polyols. Polyether polyols include, for example, polymers of propylene oxide, ethylene oxide, 1,2-butylene oxide, tetramethylene oxide, block copolymers thereof and / or random copolymers and the like. Of particular interest are homopolymers of poly (propylene oxide), random copolymers of propylene oxide and ethylene oxide in which the content of poly (ethylene oxide) is, for example, from about 1 to about 30% by weight, polymers of poly (propylene oxide) with terminal groups of ethylene oxide and random copolymers of propylene oxide and ethylene oxide with terminal groups of ethylene oxide. For applications in foams of raw material in the form of a sheet, such polyethers preferably contain 2-4, especially 2-3, mainly secondary hydroxyl groups per molecule and have an equivalent mass per hydroxyl group from about 400 to about 3000, especially from about 800 up to about 1750. For applications in highly elastic foams of raw material in the form of a sheet and in molded foams, such polyethers preferably contain 2-4, especially 2-3, mainly primary hydroxyl groups per molecule and have an equivalent weight su per hydroxyl group from about 1000 to about 3000, especially from about 1200 to about 2000. Simple polyether polyols can have a low degree of terminal unsaturation (for example, less than 0.02 meq / g or less than 0.01 meq / g), for example, those prepared using so-called double metal cyanide (DMC) catalysts, as described, for example, in US Pat. Nos. 3,278,457, 3,278,458, 3,278,459, 3,404,109, 3,427,256, 3,427,334, 3,427,335, 5,470,813 and 5,627,120. Polyester polyols are usually contain about 2 hydroxyl groups per molecule and have an equivalent mass per hydroxyl group ppu about 400-1500. Polymer polyols of various kinds may also be used. Polymer polyols include dispersions of polymer particles, such as polymer particles of polyurea, urea-polyurethane, polystyrene, polyacrylonitrile and a copolymer with acrylonitrile, in a polyol, usually in a simple polyether polyol. Suitable polymeric polyols are described in US patents 4,581,418 and 4,574,137.

When additional polyols of high equivalent weight are used, the hydroxymethyl-containing polyester polyol may comprise at least 10%, at least 25%, at least 35%, at least 50%, or at least 65% of the total weight of all high equivalent polyols masses. The hydroxymethyl-containing polyester polyol may comprise 75% or more, 85% or more, 90% or more, 95% or more, or even 100% of the total weight of all high equivalent weight polyols. For example, the hydroxymethyl-containing polyester polyol (s) may comprise 20-65%, 35-65%, 65-100%, or 80-100% of the total weight of the polyol (s) of high equivalent weight.

The polyol component may contain one or more crosslinking agents in addition to the high equivalent weight polyols described above. However, in many cases, it is preferable to use reduced amounts of crosslinking agents compared to conventional polyether polyol foam formulations. If used, suitable amounts of crosslinking agents are from about 0.1 to about 1 part by weight, especially from about 0.25 to about 0.5 part by weight per 100 parts by weight of high equivalent weight polyols. The reduced levels of crosslinkers and chain extenders used have been found to facilitate good “blowing” during which the cell walls break down and a flexible foam with good quality open pores is formed, essentially without having to open the cells mechanically. In the compositions of block block foams and highly elastic block block foams, it is often preferable to substantially exclude crosslinking agents and chain extenders, i.e. use from zero to less than 0.25 parts of crosslinking agent per 100 parts by weight of high equivalent weight polyol. Most preferably, no additional crosslinking agent is used.

For the purposes of this invention, “crosslinking agents” are materials having three or more capable of reacting with an isocyanate group per molecule and an equivalent mass of less than 400 capable of reacting with an isocyanate group. Crosslinking agents preferably contain 3-8, especially 3-4 hydroxyl, primary amino groups or secondary amino groups per molecule and have an equivalent weight of from 30 to about 200, especially from 50 to 125. Examples of suitable crosslinking agents include diethanolamine, monoethanolamine, triethanolamine, mono-, di- or three (isop opanol) amine, glycerine, trimethylol propane, pentaerythritol and the like.

The polyol component may also contain one or more chain extenders, which for the purposes of this invention means a material having two groups capable of reacting with an isocyanate group per molecule and an equivalent mass of less than 400 capable of reacting with an isocyanate group, especially from 31 to 125. Able to react with the isocyanate groups are preferably a hydroxyl, primary aliphatic or aromatic amino group or a secondary aliphatic or aromatic amino group. Examples of chain extenders include amines ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, ethylene diamine, phenylenediamine, bis (3-chloro-4-aminophenyl) methane and 2,4-diamino-3,5-diethyltoluene. If used, chain extenders are typically present in amounts of from about 1 to about 50, especially from about 3 to about 25 parts by weight per 100 parts by weight of a high equivalent weight polyol. Chain extenders are usually excluded from the composition of block foams and highly elastic block foams.

The organic polyisocyanate may be a polymeric polyisocyanate, aromatic isocyanate, cycloaliphatic isocyanate or aliphatic isocyanate. Examples of polyisocyanates include m-phenylenediisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate -1,5-diisocyanate, methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 4,4'-biphenylene-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3.3 '-dimethyl-4,4'-biphenyldiisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4', 4 "-triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate (PMDI), toluene-2,4-6-triisocyanate and 4,4'-dimethyldi enylmethane-2,2 ', 5,5'-tetraisocyanate. Preferably, the polyisocyanate is diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, PMDI, toluene-2,4-diisocyanate, toluene-2.6 -diisocyanate or mixtures thereof. Diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate and mixtures thereof are generally called "MDI" and all of them can be used. Toluene-2,4-diisocyanate, toluene - 2,6-diisocyanate and mixtures thereof are generally referred to as “TDI”, and all of them can be used.

The amount of polyisocyanate used to make the polyurethane is usually expressed as an isocyanate index, i.e. 100-fold ratio of NCO groups to groups capable of reacting with isocyanate in the reaction mixture (including those given by water if it is used as a foaming agent). In the manufacture of conventional block foam, the isocyanate index is usually in the range of about 95 to 140, especially from about 105 to 115. In the molded foam and in the highly elastic block foam, the isocyanate index is usually in the range of about 50 to about 150, especially from about 85 to about 110.

The interaction of the polyisocyanate and the polyol component is carried out in the presence of a foaming agent. Suitable blowing agents include physical blowing agents, such as various low boiling chlorofluorocarbons, fluorocarbons, hydrocarbons and the like. Fluorocarbons and hydrocarbons having low or zero global warming or ozone depletion potentials are preferred among physical blowing agents. Chemical blowing agents that decompose or react under the conditions of the polyurethane formation reaction are also applicable. The most preferred chemical blowing agent is water, which interacts with isocyanate groups, releasing carbon dioxide and forming urea bonds. Water is preferably used as the sole blowing agent, in this case from about 1 to about 7, especially from about 2.5 to 5 parts by weight of water, usually used per 100 parts by weight of a high equivalent weight polyol. Water can also be used in combination with a physical blowing agent, especially a fluorocarbon or hydrocarbon blowing agent. In addition, a gas such as carbon dioxide, air, nitrogen or argon can be used as a foaming agent in the foaming process.

The composition of the foam also use a surfactant. A wide variety of silicone surfactants that are commonly used in the production of polyurethane foams can be used to produce the foams of this invention. Examples of such silicone surfactants are commercially available under the brand names Tegostab ™ (Th. Goldschmidt and Co.), Niax ™ (GE OSi Silicones) and Dabco ™ (Air Products and Chemicals). As discussed in more detail below, some types of silicone surfactants perform better than others in specific foam formulations that contain a high relative proportion of hydroxymethylated polyol. Moreover, the optimal surfactant for use in this invention is different from those commonly used to produce these types of polyurethane foams using conventional polyether or polyether polyols. The amount of surfactant used will vary somewhat in accordance with the particular application and surfactant used, but as a rule it will be between 0.1 and 6 parts by weight per 100 parts by weight of a high equivalent weight polyol.

The foam composition will typically contain a catalyst. The choice of a particular catalyst package will vary somewhat with the other ingredients in the foam. The catalyst can catalyze a polyol-isocyanate (gel) reaction, or a water-isocyanate (foam) reaction (when water is used as a foaming agent), or both. In the preparation of water-expandable foams, it is typical to use a mixture of at least one catalyst that promotes a foaming reaction and at least one other catalyst that promotes a gelation reaction. Compositions containing a high relative proportion of hydroxymethylated polyol tend to form denser foams than formulations containing mainly ordinary simple or complex polyether polyols. Accordingly, it is often preferable in such cases to use a reduced amount of gelling catalyst and an increased (relative to the amount of gelling catalyst) amount of a foaming catalyst compared to similar foams obtained using conventional polyether polyols.

A variety of materials are known for the catalysis of polyurethane formation reactions, including tertiary amines, tertiary phosphines, various metal chelates, acid metal salts, strong bases, various metal alkoxides and phenolates, and metal salts and organic acids. The most important catalysts are catalysts - tertiary amines and organotin catalysts. Examples of tertiary amine catalysts include trimethylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylbenzylamine, N, N-dimethylethanolamine, N, N, N ', N'-tetramethyl-1,4-butanediamine, N, N-dimethylpiperazine, 1,4-diazobicyclo-2,2,2-octane, bis (dimethylaminoethyl) ether, triethylenediamine and dimethylalkylamines, where the alkyl group contains from 4 to 18 carbon atoms. Mixtures of these tertiary amine catalysts are often used. Examples of suitable commercially available surfactants include Niax ™ A1 (propylene glycol bis (dimethylaminoethyl) ether available from GE OSi Silicones), Niax ™ B9 (N, N-dimethylpiperazine and N, N-dimethylhexadecylamine in polyalkylene oxide polyol, available from GE OSi Silicones), Dabco ™ 8264 (a mixture of bis (dimethylaminoethyl) ether, triethylenediamine and dimethylhydroxyethylamine in dipropylene glycol, available from Air Products and Chemicals) and Dabco ™ 33LV (triethylenediamine in dipropylene glycol, available from Air Products and Chemicalx-Nia) 400 (patented tertiary amine composition in / carboxylic acid salt available from GE OSi Silicones), Niax ™ A-300 (patented tertiary amine / carboxylic acid salt and triethylenediamine in water from GE OSi Silicones), Polycat ™ 58 (patented amine-based catalyst, available from Air Products and Chemicals), Polycat ™ 5 (pentamethyl diethylenetriamine available from Air Products and Chemicals) and Polycat ™ 8 (N, N-dimethylcyclohexylamine available from Air Products and Chemicals).

Examples of organotin catalysts are tin (IV) chloride, tin (II) chloride, tin (II) octanoate, tin (II) oleate, dimethyltin dilaurate, dibutyltin dilaurate, and other organotin compounds of the formula SnR _n (OR) _4-n , where R represents alkyl or aryl; and n is 0-2, and the like. Organotin catalysts are usually used in combination with one or more catalysts — tertiary amines, if at all. Organotin catalysts tend to be strong gelation catalysts; therefore, they are less preferred than tertiary amine catalysts and, if used, it is preferred in small quantities, especially in highly elastic foam compositions. Commercially available organotin catalysts of interest include Dabco ™ T-9 and T-95 catalysts (both of which are tin (II) octanoate compositions available from Air Products and Chemicals).

Catalysts are typically used in small amounts from about 0.0015 to about 5% by weight of a high equivalent weight polyol.

In addition to these components, the foam composition may contain various other optional ingredients, such as cell openers; fillers such as calcium carbonate; pigments and / or dyes, such as titanium dioxide, iron oxide, chromium oxide, azo / diazo dyes, phthalocyanines, dioxazines and soot; reinforcing agents such as fiberglass, carbon fibers, glass flakes, mica, talc and the like; biocides; preservatives; antioxidants; flame retardants and the like.

Typically, polyurethane foam is prepared by mixing a polyisocyanate and a polyol composition in the presence of a foaming agent, surfactant, catalyst (s) and other optional ingredients, when desired, under conditions such that the polyisocyanate and the polyol composition interact to form a polyurethane and / or polyurea polymer, whereas the foaming agent forms a gas that foams the reaction mixture. The foam can be formed by the so-called prepolymer method (which is described in US Pat. No. 4,390,645, for example), in which a stoichiometric excess of polyisocyanate is first reacted with high equivalent weight polyol (s) to form a prepolymer which is reacted with a chain extender in a second step and / or water until the desired foam is formed. Foaming methods (which are described, for example, in US Pat. Nos. 3,755,212, 3,849,156 and 3,821,130) are also suitable. The so-called disposable methods (which are described in US patent No. 2866744) are preferred. In such disposable methods, the polyisocyanate and all components capable of interacting with the polyisocyanate are simultaneously brought into contact with each other and forced to interact. Three commonly used disposable methods that are suitable for use in this invention include processes for producing block foams, processes for producing highly elastic block foams, and processes for producing molded foams.

Block foam is usually obtained by mixing the ingredients of the foam and distributing them on a tray or other area where the reaction mixture reacts, rises freely against the atmosphere (sometimes under a film or other flexible coating) and cures. In a typical industrial production of block polystyrene foams, the foam ingredients (or various mixtures thereof) are pumped independently to the mixing head, where they are mixed, and fed to a conveyor that is lined with paper or plastic. Foaming and curing occurs on the conveyor with the formation of a foamed mass (loaf foam). The resulting foams typically have a density of from about 1 to about 5 pounds per cubic foot (pcf = pound / cubic foot) (16-80 kg / m ³ ), especially from about 1.2 to about 2.0 pound / cubic foot (19.2-32 kg / m ³ ).

In the preferred composition of the block foam according to the invention, water is used as the main or, more preferably, the sole blowing agent, and a foam having a density of from about 1.2 to about 2.0 lb / cubic foot (19.2-32 kg / m ³ ), especially from about 1.2 to about 1.8 lb / cubic foot (19.2-28.8 kg / m ³ ). To achieve such densities, from about 3 to about 6, preferably from about 4 to about 5 parts by weight of water are used per 100 parts by weight of a high equivalent weight polyol.

It has been found that in high water block foam formulations, such as those in which the hydroxymethylated polyol is more than 50%, especially 80-100% of the total mass of high equivalent weight polyols, the foam often tends to have rough cellular structure. This problem can be overcome by using specific types of silicone surfactants. A preferred type of silicone surfactant for said block foam formulations has a siloxane backbone containing a mixture of high atomic mass polyoxyalkylene side groups having an average atomic mass of from about 1,400 to about 6,000. The siloxane backbone preferably also contains low atomic mass polyoxyalkylene side groups, having an average atomic mass of from about 300 to about 750. More preferably, the siloxane backbone contains polyoxyalkylene side groups and is high oh, and low atomic mass, which, taken together, have an average atomic mass of about 1000-2000, especially 1100-1800. The silicone surfactant preferably contains about 45-360, especially about 90-260, silicone repeating units per molecule. Preferably, about 6-30% of such silicone repeating units contain a high or low atomic mass polyoxyalkylene side group. Surfactants of these types are described, for example, in US 5145879 and EP 0712884 B1, both sources are hereby incorporated by reference. Suitably, from about 1-6, preferably from about 2-4 parts by weight of such surfactants per 100 parts by weight of high equivalent weight polyols are used.

Preferred silicone surfactants for these high water content and highly hydroxymethylated polyol block foam applications can be represented by the formula MD _x D ' _y M _y , where

each M independently represents (CH ₃ ) ₃ SiO _1/2 or R (CH ₃ ) ₂ SiO _1/2 ;

D represents (CH ₃ ) ₂ SiO _1/2 ;

D 'represents R (CH ₃ ) SiO _2/2 ;

x is 40-220, especially 85-220

y is 5-40, especially 8-40 with x / y <10, and

each R independently represents a high atomic weight polyether group or a low atomic weight polyether group, provided that a sufficient number of R groups are high atomic weight polyether groups, so that the average atomic weight of all the polyether groups is at least 1000, especially for at least 1100. High atomic weight polyether R groups preferably have a structure

- (CH ₂ ) _n (C ₂ H ₄ O) _a (CH ₂ CH (CH ₃ ) O) _b R ',

in which n is from about 3 to 10, a and b are such that ethylene oxide residues (i.e., groups —C ₂ H ₄ O—) are from 30-100%, especially 30-50% by weight of the R group, and the atomic mass of the R group is about 1400-6000, especially 3500-5000, and R 'is hydrogen, alkyl, -C (O) R ", -C (O) OR" or -C (O) NHR ", where R "represents a monofunctional group alkyl or aryl. The low atomic weight polyether R groups preferably have a structure

- (CH ₂ ) _n (C ₂ H ₄ O) _a (CH ₂ CH (CH ₃ ) O) _b R ',

in which n is from about 3 to 10, a and b are such that ethylene oxide residues (i.e., groups —C ₂ H ₄ O—) are from 30-100% by weight of the R group, the atomic mass of the R group is about 300 -750, and R 'has the above meanings.

Those surfactants in which x and y represent a particularly high value (such as an x value of 85 or more and a y value of 8 or more in the above structure) tend to have very high viscosities and therefore may mix poorly with other components of the foam composition. This problem can be overcome by thinning the surfactant with a diluent such as an aliphatic hydrocarbon, aromatic hydrocarbon, ethoxylated phenol, alkylene benzene, polyether polyol, dipropylene glycol and the like. The diluent is usually used in sufficient quantity to bring the viscosity of the surfactant mixture to below 3000 cP at 25 ° C.

Two silicone surfactants of particular interest for highly hydroxymethylated high water block foam formulations are Niax ™ L-626 and Niax ™ L-5614 surfactants, both available from GE OSi Silicones. These materials are mixtures of high molecular weight silicone surfactant and diluent.

It is also preferable to use a mixture of a tertiary amine catalyst and / or a mixture of a tertiary amine catalyst and an organotin in highly hydroxymethylated high water foam formulations. If a mixture of a tertiary amine catalyst and an organotin catalyst is used, the amount of the organotin catalyst tends to decrease slightly compared to the amounts used in high water block foam formulations based on conventional polyether polyols, especially when the hydroxymethylated polyol has an equivalent weight of about 600-800. Particularly suitable catalyst packages for highly hydroxymethylated high-water block foam formulations are tin (II) octenoate mixtures with one or more bis (dimethylaminoethyl) ether, triethylenediamine and dimethylhydroxyethylamine compounds (such as, for example, a mixture of Dabco ™ T9 or T95 catalysts and Dabco ™ 8264).

High-frequency block (HR-block) foam is obtained by methods similar to those used to obtain conventional block foam. HR-block foams are characterized by a rebound score of 55% or higher according to Bashore (Bashore rebound score) according to ASTM 3574.03. These foams tend to be prepared using slightly higher levels of catalyst compared to conventional block foams in order to reduce the energy requirements for curing the foam. Compositions of HR-block foam, foamed only with water, tend to use lower levels of water than conventional formulations of raw material in the form of a sheet, and therefore form foams of somewhat higher density. Water levels tend to be from about 2 to about 3.5, especially from about 2.5 to about 3 parts, per 100 parts of high equivalent weight polyols. Density foams typically range from about 2 to about 5 lb / cubic foot (32-80 kg / m ³ ), especially from about 2.1 to about 3 lb / cubic foot (33.6-48 kg / m ³ ) .

It has been found that water-expandable HR-block foams obtained with large quantities of hydroxymethylated polyol (80-100% by weight of all polyols) tend to form “densified” foams with a high relative fraction of closed cells if the catalyst bags are not optimized. Commercial grade HR block foams typically exhibit “blowing” during cure when the cell walls open and the foaming agent is released. This opening of the cell walls balances the internal pressures of the cells with atmospheric pressure and thus prevents or reduces shrinkage when the foam cools. Highly hydroxymethylated polyol HR foamable formulations of the HR block foam are most suitable so as not to produce the indicated “blowing”. This is, in particular, the case when the hydroxymethylated polyol has an equivalent weight of less than about 700. As a result, these foams are prone to shrinkage unless additional measures are taken to open the cells. Such additional measures include, for example, using cell openers in the foam or crushing the foam to mechanically open the cells.

Probably, these problems relate to inconsistencies in the relative rates of the reactions of "gelation" and "foaming" when the foam cures. It was found that measures that slow down the gelation reaction make it possible to obtain HR-block foams with compositions with a highly hydroxymethylated polyol with good “blowing” and, therefore, with a high relative fraction of open cells and minimal or no shrinkage. Such measures include (a) the use of a mixture of toluene diamine containing 25% -40% of the 2,4-isomer; (b) essentially excluding crosslinking agents from the composition; (c) the use of a hydroxymethylated polyol with an equivalent weight of more than 700, especially more than 725, up to about 1000, and (d) essentially eliminating organometallic (especially organotin) catalysts from the composition. Each of these measures can be used as the only one, or two or more of them can be used in combination. It is preferable that the water-expandable composition of the HR-block foam with a highly hydroxymethylated polyol, substantially devoid of crosslinking agents, contains hydroxymethylated polyols of an equivalent mass of 725 or higher, especially up to an equivalent mass of 1000, and substantially devoid of organometallic catalysts, especially substantially devoid of organotin catalysts.

Catalysts that are particularly suitable for these water-expandable, high hydroxymethylated foam formulations include a mixture of N, N-dimethylpiperazine and N, N-dimethylhexadecylamine (such as Niax ™ B9, available from GE OSi Silicones) and a mixture of triethylenediamine (such as Dabco ™ 33LV available from Air Products and Chemicals) with a bis (dimethylaminoethyl) ether (such as Niax ™ A1 from GE OSi Silicones). A mixture of about 4-8 parts, especially 5-6 parts, of a 33% solution of triethylenediamine per 1 part of a 70% solution of simple bis (dimethylaminoethyl) ether is a particularly suitable catalyst package for such HR block foam formulations. Such a mixture is advantageously used in an amount of from about 0.2 to about 0.5 parts per 100 parts by weight of high equivalent weight polyols.

It has also been found that silicone surfactants, which are commonly used in traditional HR block foam formulations, can usually also be used in the hydroxymethylated polyol HR block foam formulations of the invention. This may even be the case with water-expandable formulations containing high levels (80-100% by weight of all polyols) of hydroxymethylated polyols. Such suitable surfactants include polysiloxane polymers having terminal or side polyether groups. A suitable class of polysiloxane polymers includes those containing up to about 20 siloxane units (substituted or unsubstituted) per molecule. Such polysiloxane polymers preferably contain about one lateral polyether group for every 3-8 siloxane units. The polyether side groups are preferably polymers of ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide. Examples of commercially available HR foam surfactants that are applicable include Dabco ™ DC2585, Dabco ™ DC5043 and Dabco ™ DC5180 surfactants, available from Air Products, Niax ™ U-2000 surfactant, available from GE OSi Silicones, and Tegostab ™ B 8681, Tegostab ™ B4351, Tegostab ™ B8631, Tegostab ™ B8707 and Tegostab ™ B8715 surfactants, available from Th. Goldschmidt.

A molded foam can be prepared according to the invention by transferring reagents (a polyol composition including a hydroxymethyl complex polyester polyol, a polyisocyanate, a foaming agent and a surfactant) into a closed mold where a foaming reaction takes place to produce a molded foam. Either the so-called "cold forming" process can be used, in which the mold is not pre-heated to temperatures noticeably above ambient temperature, or the "hot molding" process, in which the mold is heated to stimulate curing. Cold forming processes are preferred to produce a highly elastic molded foam. Densities of molded foams tend to range from 2.0 to about 5.0 pounds per cubic foot (32-80 kg / m ³ ).

The polyols of the invention are also useful for producing foam by a mechanical foaming process. In such processes, air, nitrogen, or another gas is introduced by beating into a reaction mixture containing high equivalent weight polyol (s), polyisocyanate and optionally catalysts, surfactants as previously described, crosslinking agents, chain extenders, and other components. The foamed reaction mixture is then usually applied to a substrate, where it is allowed to cure to form a viscous cellular layer. A particularly important application of foaming is the formation of carpeting with an attached polyurethane elastic pad. Such gasketed carpet processes are described, for example, in US Pat. Nos. 6372810 and 5908701.

The foam according to the invention exhibits various useful and unexpected properties, especially in comparison with traditional polyether polyol foam. The foam of the invention tends to exhibit improved resistance to ultraviolet radiation. The foam according to the invention also exhibits a tendency to have an increased resistance to so-called gas bleaching, which is the result of exposure to NO _x compounds, which are usually present in flue gases. In addition, the foam of the invention often exhibits improved heat resistance.

The foam according to the invention is applicable as gaskets for upholstered furniture, car seats, car dashboards, for packaging, other applications for softening and controlling energy, for carpet backing, sealing and other purposes for which traditional polyurethane foams are used.

The following examples are presented to illustrate the invention, but are not intended to limit its essence. All parts and percentages are by weight unless otherwise indicated.

Examples 1-9

Examples 1-9 of flexible “boxed” (tare) polyurethane foams are made from the polyurethane composition shown in Table 1. Hydroxymethylated polyols comprise from 20 to 65% of the total mass of high equivalent weight polyols in these compositions.

The hydroxymethylated polyols used in examples 1-6 are as follows:

Hydroxymethylated polyol A: a polyester obtained by reacting 9, (10) -hydroxymethyl stearate (obtained by hydroxyformylation and reduction of methyl oleate) with a poly (ethylene oxide) triol of molecular weight 625 in a molar ratio of 6.51: 1 using 1012 ppm tin octanoate (II) (City Chemical Co.) as a catalyst. The resulting polyester has a viscosity of 2920 cP at 25 ° C. and a hydroxyl equivalent mass (end group analysis) of 850. M _n and M _w are measured after removal of unreacted starting materials (mainly the initiator compound) from the polyester polyol. The polyester has M _n 3118, M _w 5295 and a polydispersity of 1.7. Hydroxymethylated polyol A has an average of approximately 3.67 hydroxyl groups per molecule. The hydroxymethylated polyol A corresponds to structure I, where X represents —O— and groups A are groups A1, in which m is 7 or 8 and n is 8 or 7. On average, the polyester contains about 7.9 groups A per polyester molecule.

Hydroxymethylated Polyol B: a polyester obtained by reacting a mixture of hydroxymethylated soybean fatty acids and 9, (10) -hydroxymethyl stearate with a poly (ethylene oxide) triol of molecular weight 625 at a molar ratio of 5.99: 1 using 827 ppm tin octanoate ( II) (City Chemical Co.) as a catalyst. The obtained polyester has a viscosity of 3720 cP at 25 ° C and an equivalent hydroxyl mass of 761, M _n 2678, M _w 4270 and a polydispersity of 1.59. Hydroxymethylated polyol B has an average of approximately 3.5 hydroxyl groups per molecule. The hydroxymethylated polyol B corresponds to structure I, where X represents —O— and n = 3. It has an average of approximately 6.2 A groups per molecule. Groups A are represented by a mixture containing mainly groups A1, in which m + n is 13 or 15, groups A2, in which v + r + s is 14, groups A3, in which v + r + s + t is 13 , groups A4, in which w is 14 or 16, and groups A5. Of the total number of groups A, groups A1 make up about 33.4%, groups A2 make up about 36.2%, groups A3 make up about 2.2%, groups A4 make up about 22.2% and groups A5 make up about 5.9%. mass (and approximately equivalent molar percent). The average hydroxyl functionality of groups A is about 1.09 and the average weight of groups A is about 333.

Hydroxymethylated Polyol C: A polyester obtained by reacting a mixture of hydroxymethylated soybean fatty acids with a poly (ethylene oxide) triol of molecular weight 625 in a molar ratio of 6.03: 1 using 701 ppm tin (II) octanoate (City Chemical Co.) as a catalyst. The resulting polyester has a viscosity of 3450 cP at 25 ° C., a hydroxyl equivalent mass of 755, M _n 2858, M _w 4304 and a polydispersity of 1.51. Hydroxymethylated polyol C has an average of approximately 3.5 hydroxyl groups per molecule. It has an average of approximately 6.7 group A per molecule. The hydroxymethylated polyol C corresponds to structure I, where X represents —O— and n = 3. Groups A are represented by a mixture containing mainly groups A1, in which m + n is 13 or 15, groups A2, in which v + r + s is 14, groups A3, in which v + r + s + t is 13 , groups A4, in which w is 14 or 16, and groups A5. Of the total number of groups A, groups A1 make up about 33.3%, groups A2 make up about 36.3%, groups A3 make up about 2.2%, groups A4 make up about 22.2% and groups A5 make up about 5.9% by mass (and approximately the same molar percent). The average hydroxyl functionality of groups A is about 1.09 and the average weight of groups A is about 333.

Hydroxymethylated polyol D: a polyester obtained by reacting a mixture of hydroxymethylated soybean fatty acids and 9, (10) -hydroxymethyl stearate with a poly (ethylene oxide) triol of molecular weight 625 at a molar ratio of 5.98: 1 using 1365 ppm tin octanoate ( II) (City Chemical Co.) as a catalyst. The resulting polyester has a viscosity of 4100 cP at 25 ° C., a hydroxyl equivalent mass of 754, M _n 2615, M _w 4342 and a polydispersity of 1.66. The hydroxymethylated polyol D has an average of approximately 3.5 hydroxyl groups per molecule. It has an average of approximately 5.9 group A per molecule. The hydroxymethylated polyol D corresponds to structure I, where X represents —O— and n = 3. Groups A are represented by a mixture containing mainly groups A1, in which m + n is 13 or 15, groups A2, in which v + r + s is 14, groups A3, in which v + r + s + t is 13 , groups A4, in which w is 14 or 16, and groups A5. Of the total number of groups A, groups A1 make up about 33.9%, groups A2 make up about 39.1%, groups A3 make up about 2.9%, groups A4 make up about 19.1% and groups A5 make up about 5.0% for mass (and approximately the same molar percent). The average hydroxyl functionality of groups A is about 1.17 and the average weight of groups A is about 336.

Hydroxymethylated Polyol E: A polyester obtained by reacting hydroxymethylated soya fatty acids with a poly (ethylene oxide) triol of molecular weight 625 at a molar ratio of 5.95: 1 using 891 ppm tin (II) octanoate (City Chemical Co.) as a catalyst. The resulting polyester has a viscosity of 2730 cP at 25 ° C., a hydroxyl equivalent mass of 904, M _n 2347, M _w 3612 and a polydispersity of 1.54. The hydroxymethylated polyol E has an average of about 2.6 hydroxyl groups per molecule. It contains an average of approximately 5.2 groups A per molecule. The hydroxymethylated polyol E corresponds to structure I, where X represents —O— and n = 3. Groups A are represented by a mixture containing mainly groups A1, in which m + n is 13 or 15, groups A2, in which v + r + s is 14, groups A3, in which v + r + s + t is 13 , groups A4, in which w is 14 or 16, and groups A5. Of the total number of groups A, groups A1 make up about 37.3%, groups A2 make up about 32.5%, groups A3 make up about 1.8%, groups A4 make up about 25.2% and groups A5 make up about 3.2%. mass (and approximately the same molar percent). The average hydroxyl functionality of groups A is about 1.02 and the average weight of groups A is about 329.

Examples 1-9 of polyurethane foams are prepared using the following general procedure. All components, with the exception of polyisocyanate and an organotin catalyst, are separately measured and weighed into a metal bowl with a capacity of one quart. The contents are pre-mixed for 15 seconds at 1800 rpm using a pin type mixer. The tin catalyst discharged by volume is then added to the mixed components and mixed for an additional 15 seconds at 1800 rpm. The polyisocyanate is then added to the bowl and vigorously stirred for 3 seconds at 2400 rpm. The contents of the bowl are then poured into a 15 "× 15" × 10 "(45 × 45 × 25 cm) wooden box lined with a plastic bag inside. The foam caravans are allowed to cure overnight under a ventilated hood. They are then stored for storage under ambient conditions. and subjected to the assessment of physical properties using the ASTM test method, designated D 3574-95, with the results shown in table 1.

Table 1 Example No. one 2 3 four 5 6 7 8 9 Components Simple polyether polyol A1 80 65 fifty fifty fifteen 35 65 fifty 65 Simple polyether polyol A2 0 0 0 0 35 0 0 0 0 Hydroxymethylated Polyol A twenty 35 fifty 0 0 0 0 0 0 Hydroxymethylated Polyol B 0 0 0 fifty 0 0 0 0 0 Hydroxymethylated Polyol C 0 0 0 0 fifty fifty 0 0 0 Hydroxymethylated Polyol D 0 0 0 0 0 0 35 fifty 0 Hydroxymethylated Polyol E 0 0 0 0 0 0 0 0 35 Water 4,5 4,5 4,5 6 4,5 4,5 4,5 4,5 4,5 Amine A ³ Catalyst 0.12 0.12 0.12 0.1 0.12 0.12 0.12 0.12 0.12 Silicone Surfactant A ⁴ one one one one one one one one one Silicone Surfactant B ⁵ 0 0 0 0 0 one 0 0 0 Organotin catalyst A ⁶ 0.4 0.4 0.4 0.35 0.32 0.32 0.4 0.5 0.7 TDI-80 ⁷ 57.8 58.2 58.5 75.1 57.5 59,4 58.4 58.9 57.5 Isocyanate index 110 110 110 110 110 110 110 110 110 The properties Blowing with 96 95 94 107 93 88 126 105 95 Airflow, cfm (l / s) 4.2 (1.97) 4.3 (2.02) 3.3 (1.55) 4.3 (2.02) 4.0 (1.88) N.D. 4.3 (2.02) 2.5 (1.17) 2.6 (1.22) Shrinkage under compression 90%,% 3,7 4.3 4.4 N.D. N.D. N.D. 4.2 4.9 4.3 Density, pcf (kg / m ³ ) 1.44 (23.0) 1.54 (24.6) 1.51 (24.2) 1.15 (18.4) 1.48 (23.7) N.D. 1.48 (23.7) 1.41 (22.6) 1.40 (22.4) 25% IFD, lb (N / 323 cm ² ) 39.8 (177) 41.3 (184) 43.2 (192) 33.5 (149) 37.6 (167) N.D. 39.2 (174) 47.2 (210) 44.9 (200) 65% IFD, lb (N / 323 cm ² ) 71.6 (319) 76.8 (342) 82.1 (365) 78.8 (351) 92.3 (411) N.D. 76.3 (339) 92.2 (410) 84.3 (375) Directing factor 27.6 26.8 28.6 29.1 25,4 N.D. 26.5 33.5 32.1 Elasticity,% 38 37 36 34 31 N.D. thirty 33 33 Tensile psi (kPa) 12.7 (87.5) 12.5 (86.1) 12.1 (83.4) N.D. N.D. N.D. 12.2 (84.1) 13.3 (91.6) 12.8 (88.2) Gap, pli (N / m) 1.7 (297) 1.7 (297) 1.6 (280) N.D. N.D. N.D. 1.4 (245) 1.0 (175) 1.3 (227) Elongation,% 104 90 74 N.D. N.D. N.D. 69.5 67.8 83.7

Notes to table 1: ND - not defined. ¹ With an average functionality of 2.7 and a molecular weight of 3100, a random copolymer of 87% by weight of propylene oxide and 13% by weight of ethylene oxide, available as Voranol ™ 3137 polyol from Dow Chemical. ² Polymer polyol containing simple polyether polyol A as the main polyol and 43 wt.% Styrene / acrylonitrile solids, available as Voranol ™ 3943A from Dow Chemical Company. ³ Optimized amine catalytic mixture containing bis (dimethylaminoethyl) ether, triethylenediamine and dimethylhydroxyethylamine, available as a D-8264 catalyst from Air Products & Chemicals, Inc. ⁴ Silicone surfactant available as DC5160 from Air Products & Chemicals, Inc. ⁵ Silicone surfactant available as L-626 from GE OSi Silicones. 6 Tin (II) octanoate catalyst, available as T-95 catalyst from Air Products & Chemicals. ⁷ A mixture of 80/20 of the 2,6- and 2,4-isomers of toluene diisocyanate.

Examples of foams 1-9 demonstrate that good quality foams can be prepared using conventional catalyst / surfactant packages when the hydroxymethylated polyol is from about 20 to 65% by weight of high equivalent weight polyols. In all cases, “blowing” occurs during the foaming process, resulting in a good open-cell foam that does not shrink when it cools.

When the content of hydroxymethylated polyol is increased to 65% by weight of high equivalent weight polyols, some coarsening of the cellular structure is observed when the surfactant DC5160 (silicone surfactant A) is used alone. In Example 6, this is overcome by the addition of some surfactant L626. Surfactant L626 is probably a mixture of a silicone surfactant and a diluent in which the surfactant has the structure

MD _x D ' _y M,

where each M independently represents (CH ₃ ) ₃ SiO _1/2 or R (CH ₃ ) ₂ SiO _1/2 ; D represents (CH ₃ ) ₂ SiO _1/2 ; D 'represents R (CH ₃ ) SiO _2/2 ; x is 85-220, y is 8-40 and the R groups are mixtures of 1400-6000 polyether groups of atomic mass having the structure

- (CH ₂ ) _n (C ₂ H ₄ O) _a (CH ₂ CH (CH ₃ ) O) _b R ',

in which n is from about 3 to 10, a and b are such that ethylene oxide residues (i.e., groups —C ₂ H ₄ O—) are from 30-100%, especially 30-50% by weight of the R group, and polyether groups of atomic mass 300-750 having a structure

- (CH ₂ ) _n (C ₂ H ₄ O) _a (CH ₂ CH (CH ₃ ) O) _b R ',

in which n is from about 3 to 10, and a and b are such that ethylene oxide residues (i.e., groups —C ₂ H ₄ O—) are from 30-100% by weight of group R.

Examples 10-15

Examples 10-15 of flexible “boxed” polyurethane foams are made from the polyurethane compositions shown in Table 2. The foams are prepared and tested essentially in the same manner as described in Examples 1-9. In these foams, hydroxymethylated polyols are the only component of high equivalent weight polyol.

Hydroxymethylated polyol C is described above.

Hydroxymethylated polyol F: a polyester obtained by reacting a mixture of hydroxymethylated soybean fatty acids, 9, (10) -hydroxymethyl stearate and methyl stearate with a poly (ethylene oxide) triol of molecular weight 625 in a molar ratio of ~ 6: 1 using tin (II) oleate as catalyst. The obtained polyester has a viscosity of 3440 cP at 25 ° C. and a hydroxyl equivalent mass of 661, M _n 3163, M _w 4560 and a polydispersity of 1.47. The hydroxymethylated polyol F has an average of approximately 4.8 hydroxyl groups per molecule. It has an average of approximately 7.6 A groups per molecule. The hydroxymethylated polyol F corresponds to structure I, where X represents —O— and n = 3. Groups A are represented by a mixture containing mainly groups A1, in which m + n is 13 or 15, groups A2, in which v + r + s is 14, groups A3, in which v + r + s + t is 13 , groups A4, in which w is 14 or 16, and groups A5. Of the total number of groups A, groups A1 make up about 34.1%, groups A2 make up about 36.0%, groups A3 make up about 3.1%, groups A4 make up about 23.7% and groups A5 make up about 3.0% for mass (and approximately the same molar percent). The average hydroxyl functionality of groups A is about 1.10 and the average weight of groups A is about 333.

Hydroxymethylated Polyol G: a polyester obtained by reacting a mixture of hydroxymethylated soybean fatty acids, 9, (10) -hydroxymethyl stearate and methyl stearate with a poly (ethylene oxide) triol of molecular weight 625 in a molar ratio of ~ 6: 1 using tin (II) oleate as catalyst. The obtained polyester has a viscosity of 3168 cP at 25 ° C, an equivalent hydroxyl mass of 660, M _n 3770, M _w 4647 and a polydispersity of 1.47. The hydroxymethylated polyol G has an average of approximately 4.8 hydroxyl groups per molecule. It has an average of approximately 7.6 A groups per molecule. The hydroxymethylated polyol F corresponds to structure I, where X represents —O— and n = 3. Groups A are represented by a mixture containing mainly groups A1, in which m + n is 13 or 15, groups A2, in which v + r + s is 14, groups A3, in which v + r + s + t is 13 , groups A4, in which w is 14 or 16, and groups A5. Of the total number of groups A, groups A1 make up about 34.2%, groups A2 make up about 36.2%, groups A3 make up about 3.1%, groups A4 make up about 23.4% and groups A5 make up about 3.0% for mass (and approximately the same molar percent). The average hydroxyl functionality of groups A is about 1.10 and the average weight of groups A is about 333.

table 2 Example No. 10 eleven 12 13 fourteen fifteen Components Hydroxymethylated Polyol C one hundred one hundred one hundred 0 0 0 Hydroxymethylated Polyol F 0 0 0 one hundred one hundred 0 Hydroxymethylated Polyol G 0 0 0 0 0 one hundred Water 4,5 4,5 4,5 4,5 4,5 4,5 Amine A ¹ Catalyst 0.12 0.12 0.12 0.12 0.12 0.12 Silicone Surfactant B ² 3 3 3 3 3 3 Organotin catalyst A ³ 0.38 0.28 0.38 0.28 0.22 0.28 TDI-80 ⁴ 57.4 63.1 68.8 62,4 62,4 62,4 Isocyanate index one hundred 110 120 110 110 110 The properties Blowing Airflow, cfm (l / s) N.D. 87 104 97 103 109 Density, psi (kg / m ³ ) 0.91 (0.43) 0.63 (0.30) 0.31 (0.15) 1.16 (0.55) 1.15 (0.54) 1.37 (0.64) 25% IFD, lb (N / 323 cm ² ) 1.56 (25.0) 1.52 (24.3) 1.48 (23.7) 1.38 (22.1) 1.38 (22.1) 1.38 (22.1) 65% IFD, lb (N / 323 cm ² ) 39.6 (176) 37.8 (168) 49.6 (221) 42.7
(190) 42.1 (187) 39.2
(174) Directing factor 87.9 (391) 93.6 (417) 95.5
(425) 87.9 (391) 90.0 (400) 90.2 (401) Elasticity,% 25,4 24.9 33.5 30.9 30.5 28,4 Tensile Strength, pli (N / m) 28 29th 32 26 26 thirty Tensile Strength, psi (kPa) N.D. N.D. N.D. 0.5 (8.9) 0.5 (8.9) 0.7 (12.5) Elongation,% N.D. N.D. N.D. 7.2 (49.6) 7.0 (48.2) 9.6 (62.0) ^1-4 See notes 3, 5, 6 and 7 of table 1.

Examples 10-15 demonstrate that good quality foams can be prepared when the hydroxymethylated polyol is the only high equivalent weight polyol. Surfactant L-626 (silicone surfactant B described in Examples 1-9) provides a foam with a fine mesh structure and good appearance. In these formulations, some conventional block-foam surfactants tend to produce foams having a deteriorated cellular structure. The decrease in the amount of organotin catalyst (gelation catalyst) in Examples 13, 14 and 15 (as compared with Examples 10, 11 and 12) results in better blowing, resulting in increased air flow and lower foam density.

Examples 16-21

Examples 16-21 of flexible polyurethane foams of raw material in the form of a sheet are made from polyurethane compositions shown in table 3. Hydroxymethylated polyols comprise 20-50% of the total mass of polyols of high equivalent weight in these compositions. Foams are produced continuously on an industrial machine for producing block foams (Polymech or UBT), characterized by a reciprocating mixing head and separate injection under high pressure of all flows, with the exception of polyols. Polyols are mixed and injected as a single mixture. The temperatures of the polyol and isocyanate are maintained at about 23 ° C. The yield of polyol is 20 kg / min.

Hydroxymethylated Polyol H: A polyester obtained by reacting a mixture of hydroxymethylated soybean fatty acids with a poly (ethylene oxide) triol of molecular weight 625 at a molar ratio of ~ 10: 1 using ~ 1000 ppm tin (II) octanoate (City Chemical Co.) as a catalyst. Polyol is obtained in two batches, which are mixed. The mixed polyester has a viscosity of 2800-3010 cP at 25 ° C, a hydroxyl equivalent mass of ~ 830, M _n ~ 3065, M _w ~ 5085 and a polydispersity of ~ 1.65. The hydroxymethylated polyol H has an average of approximately 3.7 hydroxyl groups per molecule. The hydroxymethylated polyol H corresponds to structure I, where X represents —O— and n = 3. The hydroxymethylated polyol A corresponds to structure I, where X represents —O— and groups A are groups A1 in which m is 7 or 8 and n is 8 or 7. On average, the polyester contains about 7.7 groups A per molecule.

Hydroxymethylated polyol I: a polyester obtained by reacting a mixture of hydroxymethylated soybean fatty acids and 9, (10) -hydroxymethyl stearate with a poly (ethylene oxide) triol of molecular weight 625 at a molar ratio of ~ 6: 1 using ~ 1000 ppm tin octanoate ( II) (City Chemical Co.) as a catalyst. Polyol is obtained in two batches, which are mixed. The mixed polyester has a viscosity of 3570-3940 cP at 25 ° C, a hydroxyl equivalent mass of ~ 775, M _n ~ 2625, M _w ~ 4330 and a polydispersity of ~ 1.65. Hydroxymethylated polyol I has an average of approximately 3.5 hydroxyl groups per molecule. It has an average of about 6.1 groups A per molecule. The hydroxymethylated polyol I corresponds to structure I, where X represents —O— and n = 3. Groups A are represented by a mixture containing mainly groups A1, in which m + n is 13 or 15, groups A2, in which v + r + s is 14, groups A3, in which v + r + s + t is 13 , groups A4, in which w is 14 or 16, and groups A5. Of the total number of groups A, groups A1 make up about 33.8%, groups A2 make up about 39.0%, groups A3 make up about 2.8%, groups A4 make up about 19.3% and groups A5 make up about 5.1% for mass (and approximately the same molar percent). The average hydroxyl functionality of groups A is about 1.16 and the average weight of groups A is about 336.

Table 3 Example No. 16 17 eighteen 19 twenty 21 Components Simple polyether polyol A ¹ 80 65 fifty 80 65 fifty Hydroxymethylated Polyol H twenty 35 fifty 0 0 0 Hydroxymethylated Polyol I 0 0 0 twenty 35 fifty Water 4,5 4,5 4,5 4,5 4,5 4,5 Amine A ² Catalyst 0.12 0.12 0.12 0.12 0.12 0.12 Silicone Surfactant A ³ one one one one one one Organotin catalyst B ⁴ 0.2 0.2 0.2 0.16 0.14 0.12 TDI-80 ⁵ 57.8 58.1 58.4 57.4 58.4 58.8 Isocyanate index 110 110 110 110 110 110 The properties Density, kg / m ³ 21.1 21.3 21,4 22.8 23,4 22.5 Shrinkage under compression 75%,% N.D. N.D. N.D. 3,5 4.7 7.8 CFD, 40%, kPa 3.9 4.3 4,5 N.D. N.D. N.D. IFD, 40%, kPa 156.2 168.4 175.9 166.6 167.5 187.4 SAG factor 2.7 2,8 2.9 2.7 2.7 2.9 Hysteresis,% 45 49 53 N.D. N.D. N.D. Elasticity,% 40 36 36 42 39 39 Directing factor 7.4 7.9 8.2 7.3 7.2 8.3 Airflow, cfm (l / s) 3.1 (1.46) 2.4 (1.13) 2.1 (0.99) 4.5 (2.12) 4.1 (1.93) 4.1 (1.93) Tensile Strength (kPa) 89 80 78 60 61 75 Elongation,% 142 128 102 279 266 194 Tensile strength (N / m) 426 337 309 88 93 71 ^1-3.5 See notes 1, 3, 4, and 7 to table 1. ⁴ Tin (II) octanoate catalyst, available as T-9 catalyst from Air Products and Chemicals.

Examples 22-31

Highly elastic “box” block block foams are prepared and evaluated essentially in the same manner as described in Examples 1-9 using the formulations shown in Table 4. The results are presented in Table 4. Density and CFD are measured according to DIN EN ISO 845-95 and 3386-1-98, respectively. Air flow, tear and elasticity are measured according to ASTM D 3671-03. Elasticity and elongation are measured according to ISO 1798-97. Compression shrinkage is measured according to ISO 1856-80.

Hydroxymethylated Polyol J: A polyester obtained by reacting hydroxymethylated soybean fatty acids with a poly (ethylene oxide) triol of molecular weight 625 at a molar ratio of ~ 8: 1 using ~ 1000 ppm tin (II) octanoate (City Chemical Co.) as a catalyst. The polyester has a viscosity of 6680 cP at 25 ° C, a hydroxyl equivalent mass of ~ 620, M _n ~ 3547, M _w ~ 5443 and a polydispersity of ~ 1.57. The hydroxymethylated polyol J has an average of approximately 5.7 hydroxyl groups per molecule. It has an average of approximately 8.45 groups A per molecule. The hydroxymethylated polyol J corresponds to structure I, where X represents —O— and n = 3. Groups A are represented by a mixture containing mainly groups A1, in which m + n is 13 or 15, groups A2, in which v + r + s is 14, groups A3, in which v + r + s + t is 13 , groups A4, in which w is 14 or 16, and groups A5. Of the total number of groups A, groups A1 make up about 35.5%, groups A2 make up about 41.4%, groups A3 make up about 2.4%, groups A4 make up about 18.5% and groups A5 make up about 2.2%. mass (and approximately the same molar percent). The average hydroxyl functionality of groups A is about 1.20 and the average weight of groups A is about 334.

Hydroxymethylated Polyol K: A polyester obtained by reacting hydroxymethylated soybean fatty acids with a poly (ethylene oxide) triol of molecular weight 625 at a molar ratio of ~ 5.5: 1 using ~ 1000 ppm tin (II) octanoate (City Chemical Co. ) as a catalyst. The polyester has a viscosity of 2320 cP at 25 ° C, a hydroxyl equivalent mass of ~ 743, M _n ~ 2738, M _w ~ 3995 and a polydispersity of ~ 1.46. The hydroxymethylated polyol K has an average of approximately 3.7 hydroxyl groups per molecule. It has an average of about 6.5 A groups per molecule. The hydroxymethylated polyol K corresponds to structure I, where X represents —O— and n = 3. Groups A are represented by a mixture containing mainly groups A1, in which m + n is 13 or 15, groups A2, in which v + r + s is 14, groups A3, in which v + r + s + t is 13 , groups A4, in which w is 14 or 16, and groups A5. Of the total number of groups A, groups A1 make up about 40.9%, groups A2 make up about 29.4%, groups A3 make up about 1.8%, groups A4 make up about 26.6% and groups A5 make up about 1.3%. mass (and approximately the same molar percent). The average hydroxyl functionality of groups A is about 1.0 and the average weight of groups A is about 326.

Table 4 Example # 22 23 24 25 26 27 28 29th thirty 31 Components Polymer Polyol B ¹ twenty 0 0 0 0 0 0 0 0 0 Cell opener A ² 0.5 0.5 0.5 1,0 1,0 1,0 1,0 0 0 0 Hydroxymethylated Polyol J 80 one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred 0 Hydroxymethylated Polyol K 0 0 0 0 0 0 0 0 0 one hundred Water 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Diethanolamine, 99% 1,5 1,5 1,5 1,5 1,5 1,5 0.5 0 0 0 Amine B ³ catalyst 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0 0 0.30 Amine C ⁴ Catalyst 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0 0 0.05 Amine D ⁵ Catalyst 0 0 0 0 0 0 0 1,0 1,0 0 Organotin catalyst ⁶ 0.15 0.15 0.05 0.05 0 0 0 0 0 0 Silicone Surfactant C ⁷ 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 TDI-80 ⁸ 49 49 49 49 49 47 44 35 40 42.7 TDI-65 ³ 0 0 0 0 0 0 0 5 0 0 Isocyanate index 105 105 105 105 105 one hundred one hundred one hundred one hundred 105 The properties The transition time in a creamy mass, s 12 10 10 10 10 10 10 10 10 10 Rise time, s 124 105 115 115 118 120 120 145 145 135 Blowing no no no no no no no Yes Yes Yes Density, kg / m ³ 27.1 27.5 29.4 29.0 30.9 30,0 30,2 35.7 34.6 36.6 CFD, 40%, kPa 3.2 2,8 3.0 2.6 3.0 2.6 3.0 4.6 4.6 4.4 Airflow, cfm (l / s) 1.3 (0.61) 2.4 (1.13) 2.7 (1.27) 4.0 (1.88) 3.8 (1.79) 2.7 (1.27) 3.4 (1.60) 2.2 (1.03) 2.1 (0.99) 2.8 (0.94) Elasticity,% 29th 29th 25 25 25 25 25 26 26 34 Tensile strength, kPa 332 34 29th 29th 26 25 N.D. 40 41 36 Elongation,% 64 60 73 72 67 72.3 N.D. 71 75 64 Gap, N / m 117 83 120 111 95 one hundred N.D. 169 149 108 Shrinkage under compression 75%,% 7.2 8.6 4.7 4.6 5,4 3,7 N.D. 9.2 eleven fourteen Shrinkage under compression 90%,% 9.6 7.9 5.8 5.3 5.5 4.4 N.D. 12 13 twenty

Notes to table 4 : ND - not defined. ¹ Polymer polyol containing a polyether triol of molecular weight 3000 as the main polyol and 40 wt.% Styrene / acrylonitrile solids, available as Voralux ™ HL 400 polyol from Dow Chemical Company. ² ~ 7-functional random copolymer of propylene oxide and ethylene oxide equivalent weight of 1800, commercially available as Voranol® 4053 from Dow Chemical. ³ 33% triethylenediamine solution available as Dabco ™ 33LV from Air Products and Chemicals. ⁴ Bis (dimethylaminoethyl) ether catalyst, commercially available from GE OSi Silicones as a Niax ™ A1 catalyst. ⁵ A mixture of N, N-dimethylpiperazine and N, N-dimethylhexadecylamine, commercially available as Niax ™ B9 from GE OSi Silicones. ⁶ See Note 4 to Table 3. ⁷ Tegostab B8681LF Surfactant Commercially Available from Th. Goldschmidt. ⁸ See note 7 to table 1. ⁹ A mixture of 65/35 of the 2,6- and 2,4-isomers of toluene diisocyanate.

All examples of foams 22-31 have good properties. Examples of Styrofoam 22-28 are very “compacted” foams that require strong crushing to open the cells and achieve good airflow and minimal shrinkage. None of Examples 22-28 show "blowing." Examples 24-31 illustrate various approaches to modifying the basic composition of the foam of example 23 in order to achieve blowing and reduce the need for crushing. In examples 24-28, the amount of organotin catalyst (gelation) is reduced and then eliminated, and the number of cell opener is increased. In Example 29, the gelation reaction is slowed down by using a mixture of toluene diisocyanate having a higher 2,4-isomer content, eliminating the crosslinking agent (diethanolamine) and replacing the catalyst. In Example 30, the crosslinking agent is again eliminated, the same catalyst is used as in Example 29, and the same toluene diisocyanate is used as in Examples 23-28. In both cases, the choice of catalysts allows blowing to occur, and a foam is obtained that requires only slight crushing, even if no cell opener is used. In Example 31, the exclusion of a crosslinking agent and an increase in the (foaming) catalyst of triethylenediamine (as compared with Example 23) results in an acceleration of the foaming reaction, resulting in good blowing and the need for only slight crushing.

Examples 32-40

Examples 32-40 polyurethane foams are molded polyurethane foams obtained using the following General procedure. All components, with the exception of polyisocyanate, are separately measured and weighed into a metal two-liter bowl. The contents are mixed for 20 seconds at high speed using an impeller-plus-ring type mixer. The polyisocyanate is added and vigorously stirred for three seconds. The contents of the bowl are then poured into an aluminum mold of 40 × 40 × 10 cm, which is heated at 60 ° C. Time to extract from the form 5 minutes. Foams are crushed after removal from the mold and then stored at 25 ° C and 50 relative humidity for 48 hours. The foam compositions and physical properties of the resulting foams are shown in Tables 5 and 6. CFD, tensile strength, elongation, air flow, tensile strength, elasticity and shrinkage in compression are measured according to ASTM D 3574-03. Density is measured according to DIN EN SO 3385-95. Wet shrinkage is measured according to BS 4443-7-92.

Table 5 Example No. 32 33 34 35 36 37 38 39 40 Components Simple polyether polyol B ¹ 70.00 60.00 50.00 70.00 70.00 70.00 60.00 50.00 40.00 Polymer Polyol C ² 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 Hydroxymethylated Polyol H 10.00 20.00 30.00 10.00 10.00 Hydroxymethylated Polyol I 10.00 20.00 30.00 40.00 Cell opener B ³ 1.00 Amine catalyst E ⁴ 0.30 Amine F ⁵ Catalyst 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Amine G ⁶ Catalyst 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Silicone Surfactant D ⁷ 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 Amine Catalyst B ⁸ 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 Silicone Surfactant E ⁹ 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Diethanolamine (100%) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Water 3.70 3.70 3.70 3.70 3.70 3.70 3.70 3.70 3.70 TDI-80 (index) one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred

Table 6 Styrofoam Properties 32 33 34 35 36 37 38 39 40 The density of the core, kg / m ³ 32.1 32.8 33,2 33.5 33.0 35,4 36.8 35.5 33.8 CFD, 50%, kPa 4.9 5.5 5,6 5,0 4.7 5,6 6.6 6.2 6.4 Tensile Strength, pKa 106 114 125 109 102 107 134 109 107 Elongation,% 104 101 106 105 one hundred 103 107 93 84 Tensile strength, N / m 281 271 284 255 266 223 220 237 198 Elasticity,% 58 57 55 57 61 53.5 52 48.5 43.5 Airflow, cfm (l / s) 1.61 (0.76) 2.49 (1.17) 1.68 (0.79) 2.28 (1.07) 2.62
(1.23) 1.0 (0.47) 1.7 (0.80) 1.5 (0.71) 1.3 (0.61) Fatigue loss of strength,% N.D. N.D. N.D. N.D. N.D. 32 34 37 40 Shrinkage at compression 50%,% 6.5 6.4 8.1 6.0 6.2 7 8 10 12 Shrinkage under compression 90%,% 11.3 11.3 13.5 8.7 9.7 9 10 fourteen 17 Shrinkage during compression in the wet state 70%,% 21.3 20.7 24.3 17.0 22.1 17 twenty 22 24

Notes to Table 5 : ¹ Poly (propylene oxide) with a functionality of 4.7 and an equivalent weight of 1750 with 15% end groups of ethylene oxide, available as Specflex ™ NC-632 from Dow Chemical Company. ² Polymer polyol with 40% solids (styrene / acrylonitrile) having as its main polyol poly (propylene oxide) with a functionality of 3.0 and an equivalent weight of 1580 with 17% of ethylene oxide end groups, available as Specflex ™ NC-700 from Dow Chemical. ³ Polyester-based cell opener available as Voranol ™ CP 1421 from Dow Chemical. ⁴ Amine catalyst, commercially available as Polycat ™ 58 from Air Products and Chemicals. ⁵ Proprietary tertiary amine / carboxyl salt and triethylenediamine in water mixture commercially available as Niax ™ A-300 from GE OSi Silicones. ⁶ Proprietary tertiary amine / carboxyl salt mixture of (2-dimethylaminoethyl) ether in water and a proprietary hydroxyl compound, commercially available as Niax ™ A-400 from GE OSi Silicones. ⁷ Silicone Surfactant Commercially Available as Tegostab ™ B8708 Surfactant from Th. Goldschmidt. ⁸ See Note 3 to Table 4. ⁹ Silicone surfactant commercially available as Dabco ™ DC 5164 surfactant.

Example 41. Comparative examples A and B: evaluation of gas bleaching and UV resistance

Example 7 is repeated, except that the content of the T-95 catalyst is increased to 0.55 parts by weight. The resulting foam has properties similar to those of example 7.

Comparative Example A is prepared essentially in the same manner as Example 7 using 100 parts of polyether polyol A, 4.5 parts of water, 1 part of silicone surfactant A, 0.12 parts of amine-based catalyst, 0, 4 parts of a TDI catalyst at an index of 110. Comparative Example A has a density of 1.44 pfc (23 kg / m ³ ) and an air flow of 4.5 cfm (2.1 l / s).

Comparative Example B was prepared essentially in the same manner as Example 7 using 100 parts of a ~ 3100 molecular weight polyether polyol with a ~ 2.7 functionality commercially available from Dow Chemical as Voranol ™ 3136 polyol, 4.5 parts water, 1 part silicone surfactant A, 0.12 parts of amine A-based catalyst, 0.35 parts of T-95 and TDI catalyst at index 110. Comparative Example B has a density of 1.38 pfc (22.1 kg / m ³ ) and an air flow of 5.12 cfm (2.1 l / s).

Assessment of gas bleaching is carried out on comparative examples A and B and examples 8, 13 and 41. Prepare blocks of each size 3 × 3 × 1 inch (7.5 × 7.5 × 2.5 cm). The initial color (“b” or yellow / blue on the colorimeter plus the overall color) is determined for each block using a Hunter colorimeter. All foam samples are approximately the same in yellowness (“b” value) and overall color. Each block is then suspended on a rotating carousel in a smoke chamber above a burning methane fuel source, so that the fumes from the burning fuel fill the chamber and come into contact with the foam. Comparative example A and examples 8 and 41 are tested together and comparative example B and example 13 are tested together in a separate experiment. The temperature in the chamber is maintained at about 130-140 ° F (54-60 ° C). Samples were removed after 60 minutes and yellowness and overall color were measured again. A change in color indicates discoloration caused by exposure to flue gases (which contain NO _x compounds, which are likely to be bleaching agents). The results are shown in table 7.

Table 7 Example or comp. sample no. Hydroxymethyl-Containing Polyester Polyol ΔA (common color) ΔB (yellowness) Original 1 hour Change Original 1 hour Change BUT* 0 -0.26 0.585 0.845 2.27 16.37 14.10 41 35% 0.47 0.37 -0.10 2.77 14.75 11.98 8 fifty% -0.16 0.24 0.40 1.55 13.23 11.68 AT* 0% 0.83 2.91 1,08 -1.48 6.63 8.11 13 one hundred% 0.89 0.28 -0.61 -1.49 4.74 6.23 * Not an example of an invention.

All samples of the invention show a noticeable improvement in discoloration compared to the corresponding controls. Yellowness is the most obvious color change with gas discoloration. As such, changes in yellowness, which are indicated by ΔB values, are most important. Yellowness is reduced both in absolute value and in the degree of change in the examples according to the invention.

UV resistance ratings

Examples 15 and 41 and comparative example B are evaluated for UV resistance. Foam samples are evaluated for UV resistance by measuring the color changes that occur during exposure to UV radiation. UV radiation is supplied from B 313 fluorescent tubes. Many samples are evaluated and the results are presented as the average of the samples. Color is measured with a Hunter colorimeter using yellowness (ΔB) measurements as a criterion for comparison, since yellowness is the dominant visible color change that is observed during UV degradation of polyurethane foam. The results are presented in table 8.

Table 8 Example or
cf.
sample no. % hydroxymethyl-containing polyester polyol ΔВ Primary. 1 hour 2 h 3 h In ^* 0 0.18 13.31 18.13 20.80 41 35 -0.26 9.35 13.59 16.47 fifteen one hundred -0.44 5.62 9.33 10.69 * Not an example of an invention.

Smaller numbers in columns 1, 2, and 3 hours of table 8 mean less yellowing and therefore better UV resistance. The data in table 8 indicate that the foam samples have a better UV resistance with an increase in the content of hydroxymethyl-containing polyester polyol.

Claims (9)

1. A method of obtaining a block, highly elastic block or molded polyurethane foam, comprising bringing the organic polyisocyanate into contact with a polyol composition containing a high equivalent mass polyol or a mixture of high equivalent mass polyols, in the presence of a foaming agent, a gelation catalyst and a surfactant under conditions when the polyisocyanate interacts with the polyol composition and the blowing agent forms a gas to form a cellular polyurethane and / or polymer based on limocheviny having a density from 1 to 5 pounds per cubic foot (16 to 80 kg / m ^3), wherein at least 10% by weight of polyol (s) a high equivalent weight is one or more hydroxymethyl-containing polyester polyols obtained by reacting containing a hydroxymethyl group of a fatty acid having 12-26 carbon atoms or an ester of such a containing hydroxymethyl group of a fatty acid with an initiating compound, a polyol or polyamine, having an average of at least 2 hydroxyl per other amino groups and / or secondary amino groups, such that the hydroxymethyl-containing polyester polyol contains an average of at least 1.3 repeating units derived from a hydroxymethyl-containing fatty acid or ester per total number of hydroxyl groups, primary amino groups and secondary amino groups on the compound -initiator, and containing hydroxymethyl complex polyester has an equivalent weight of at least 400 and up to 15000, and where containing hydroxymethyl complex polyester has the following structure:

where R represents the remainder of the initiator compound having n hydroxyl primary amino groups and / or secondary amino groups, where n is at least two, each X is independently —O—, —NH— or —NR′—, where R ′ is inertly substituted an alkyl, aryl, cycloalkyl or aralkyl group, p is a number from 1 to n representing the average number of [XZ] groups per hydroxymethyl complex polyester polyol molecule, Z is a linear or branched chain containing one or more groups A, provided that the average the number of groups A on my a molecule ≥1.3 is a multiple of n, and each A is independently selected from the group consisting of A1, A2, A3, A4 and A5, provided that at least some groups A are A1, A2 or A3, where A1 is represented by the formula

where B represents H or a covalent bond with a carbonyl carbon atom of another group A, m represents a number greater than 3, n is greater than or equal to zero and m + n is from 11 to 19, A2 is represented by the formula

where B represents the same as before, v represents a number greater than 3, r and s represent numbers greater than or equal to zero, with v + r + s equal to from 10 to 18; A3 is represented by the formula

where B, v, each r and s have the above meanings, t represents a number greater than or equal to zero, and the sum of v, r, s and t is from 10 to 18; A4 is represented by the formula

where w is 10-24, and A5 is represented by the formula

where R 'represents a linear or branched alkyl group which is substituted by at least one cyclic ether group and optionally one or more hydroxyl groups or other ether groups. 2. The method according to claim 1, where the equivalent mass containing hydroxymethyl complex polyester polyol is from about 700 to about 3500. 3. The method according to claim 2, where containing hydroxymethyl complex polyester polyol contains on average from about 2.5 to about 5 hydroxyl, primary amino groups or secondary amino groups per molecule. 4. The method according to claim 3, where containing hydroxymethyl complex polyester polyol is about 35-100% by weight of the polyol (polyols) of high equivalent weight. 5. The method according to claim 4, where the polyurethane foam has a density of from about 1.2 to about 2.0 pounds per cubic foot. 6. The method according to claim 5, where the blowing agent is water. 7. The method according to claim 1, where containing hydroxymethyl complex polyester polyol is about 80-100% by weight of the polyol (polyols) of high equivalent weight. 8. The method according to claim 7, where the surfactant is represented by the formula MD _x D ' _y M, where
each M independently represents (CH ₃ ) ₃ SiO _1/2 or R (CH ₃ ) ₂ SiO _1/2 ;
D represents (CH ₃ ) ₂ SiO _1/2 ;
D 'represents R (CH ₃ ) SiO _2/2 ;
x is 40-220, y is 5-40, x / y <10, and
each R independently represents a high atomic weight polyether group or a low atomic weight polyether group, provided that a sufficient number of R groups are high atomic weight polyether groups, so that the average atomic weight of all the polyether groups is at least 1000, especially for at least 1100. 9. Polyurethane foam obtained by the method according to claim 1.